The present invention relates to a cross-linked polyurethane composition and a multilayer sheet comprising a polymeric film and a cross-linked polyurethane layer. The multilayer sheet can be used to protect a surface and can in particular be used to protect a car body. Accordingly, the present invention also relates to an automobile of which at least a part of the body is protected by the multilayer sheet. The invention also relates to a method for making the multilayer sheet.
Polyurethane coatings are well known as protective coatings on various substrates to provide resistance to environmental weathering, chemical exposure, heat and abrasion. Polyurethanes are generally optically transparent and have found application in the protection of articles that have a variety of uses including both interior and exterior applications. Polyurethane coatings have further been used to cover and protect a base substrate having indicia or other decorative features thereon. Such decorative articles may have interior as well as exterior uses.
For example, WO 94/13465 describes a polyurethane based protective layer for protecting an embossed multilayer film. It is taught that a surface layer containing the reaction product of an aliphatic diisocyanate and a polyester polyol, polycarbonate polyol or polyacrylic polyol provides a good protection for interior as well as exterior uses. It is further disclosed that the polyurethane-based protective surface layer can be cross-linked or uncross-linked and can be solvent borne as well as aqueous borne.
WO 94/13496 discloses a multilayer graphic article that comprises a substrate, at least one color layer disposed thereon and a protective surface layer. The protective surface layer may comprise a polyurethane obtained from the reaction of an aromatic diisocyanate and a polyether polyol or a polyurethane obtained from the reaction of an aliphatic diisocyanate and a polyester polyol, polycarbonate polyol or polyacrylic polyol.
WO 93/24551 discloses that aqueous polyurethane dispersions can be used to produce a coating on various substrates. It is further mentioned that the they may be used for the provision of e.g. protective or decorative coatings since polyurethanes, depending on their composition, can possess many desirable properties such as good chemical resistance, water resistance, solvent resistance, toughness, abrasion resistance and durability. WO 93/24551 further discloses that polycarbonate polyol based polyurethanes can provide high performance aqueous polyurethane dispersions in terms of chemical, water, solvent and stain resistance of coatings derived therefrom. However such polycarbonate polyols are said to be expensive and the supply would not always be guaranteed.
Polyurethane protective coatings have been used on conformable films to protect parts of the body of an automobile. For example, the body of a car may need to be protected near the trunk where the body may be prone to damaging due to loading and unloading of articles. A fully satisfactory protective coating for this application has not yet been found despite the many protective coatings known in the art. Desirable properties for such a protective coating include good optical transparency, high weatherability, high heat resistance, high chemical resistance, high solvent resistance, high water resistance and high abrasion resistance. Furthermore, the protective coating desirably also has a good flexibility and can preferably be pigmented with dyes to obtain a colored protective layer without however substantially impairing the other desirable properties of the protective layer.
The present invention provides a multilayer sheet comprising a polymeric film having on a first major side a cross-linked polyurethane layer, the major part of said cross-linked polyurethane layer comprising a polycarbonate based polyurethane containing acid groups and cross-linked with a cross-linker, the polycarbonate based polyurethane comprising the reaction product of a polycarbonate polyol or a polycarbonate polyamine and an aliphatic polyisocyanate and the uncross-linked polycarbonate based polyurethane having a Koenig hardness of at least 150 seconds.
The multilayer sheet of the present invention has good abrasion and scratch resistance, high heat, solvent and weathering, resistance. Moreover, multilayer sheets with excellent optical properties such as clarity and transparency can be provided. Also, the polyurethane coating can be colored to provide colored versions of the multilayer sheets without substantially impairing the other desirable properties of the sheet. The multilayer sheets are useful in a variety of applications including both indoor as well as outdoor applications and they can be readily converted.
The present invention also provides a method of making a multilayer sheet comprising:
(i) coating a coating composition comprising a polycarbonate based polyurethane containing acid groups and a cross-linker on a major side of a polymeric film, and
(ii) cross-linking the thus obtained coating,
wherein the polycarbonate based polyurethane comprises the reaction product of a polycarbonate polyol or a polycarbonate polyamine and an aliphatic polyisocyanate and the uncross-linked polycarbonate based polyurethane having a Koenig hardness of at least 150 seconds.
The present invention further provides a cross-linked polyurethane composition comprising a polycarbonate based polyurethane containing acid groups and cross-linked with a cross-linker, the polycarbonate based polyurethane comprising the reaction product of a polycarbonate polyol or a polycarbonate polyamine and an aliphatic polyisocyanate and the cross-linked polycarbonate based polyurethane having a Koenig hardness of at least 150 seconds.
The cross-linked polyurethane layer of the multilayer sheet of the present invention comprises a major amount of a cross-linked polycarbonate based polyurethane derived from the reaction of a polycarbonate polyol or a polycarbonate polyamine and an aliphatic polyisocyanate, preferably an aliphatic diisocyanate. The polycarbonate-based polyurethane further contains acid groups, preferably carboxylic acid groups, that provide the necessary cross-linking sites to the polyurethane. Preferably, the polycarbonate-based polyurethane has an acid number of at least 15 mg KOH/g and more preferably at least 18 mg KOH/g.
The polycarbonate-based polyurethane of the polyurethane layer should have a Koenig hardness of at least 150 seconds, preferably at least 175 seconds and more preferably at least 200 seconds. It has been found that if the polycarbonate-based polyurethane does not meet the Koenig hardness, the desired chemical and heat resistance as well as the desired abrasion resistance could not be achieved. It has further been found that other polyurethanes, e.g. polyester based polyurethanes, although meeting the Koenig hardness requirement of at least 150 seconds also fail to yield a protective layer that has the desired chemical and heat resistance as well as the desired abrasion resistance.
Although it is possible to blend the polycarbonate based polyurethane with other polyurethanes such as for example polyurethanes based on polyether or polyester polyols or polycarbonate based polyurethanes with a lower Koenig hardness than 150 seconds, the cross-linked polycarbonate based polyurethane should form the major part of the polyurethane layer. In accordance with the present invention, xe2x80x9cmajor partxe2x80x9d means at least 60% by weight. Preferably, the cross-linked polycarbonate polyurethane constitutes at least 80% by weight and more preferably at least 90% by weight of the total weight of the polyurethane layer. The best results can be achieved when the cross-linked polycarbonate based polyurethane constitutes about 100% by weight of the polyurethane layer.
The polycarbonate-based polyurethane is preferably an aqueous borne dispersion. Aqueous borne dispersions of polycarbonate based polyurethanes and their method of preparation are well-known in the art and has been described in for example GB1549458 and GB1549459. Polycarbonate based polyurethanes for use in connection with the present invention are commercially available and include for example NEOREZ(trademark) R-986 and NEOREZ(trademark) R-985 available from Zeneca Resins, Frankfurt, Germany and ALBERDINGK(trademark) U 911 available from Aberdingk-Boley GmbH, Krefeld, Germany.
The polycarbonate-based polyurethane is cross-linked with a suitable cross-linker that readily reacts with the acid groups of the polycarbonate-based polyurethane. Preferably, the cross-linker allows for curing at a temperature below 100xc2x0 C. Cross-linking at low temperature is particularly desirable when the polymeric film of the multilayer-layer sheet has a low softening point. Examples of cross-linkers that can be used to cross-link the polycarbonate based polyurethane include melamines such as e.g. Cymel(trademark) 303, Cymel(trademark) 373 available from Cyanamide company, ureas, benzoguanamines such as Cymel(trademark) 1123 glycolurils such as Cymel(trademark) 1172 and multifunctional carbodiimides such as UCARLINK(trademark) XL 29 SE available from Eurochem. A particularly preferred class of cross-linkers for use in this invention are the polyfunctional aziridines. Examples of suitable polyfunctional aziridines include those disclosed in U.S. Pat. No. 3,225,013. Preferably, the polyfunctional aziridine is a trifunctional aziridine. Particular examples are trimethylol propane tris[3-aziridinyl propionate]; trimethylol propane tris[3(2-methyl-aziridinyl)-propionate]; trimethylol propane tris[2-aziridinyl butyrate]; tris(1-aziridinyl)phosphine oxide; tris(2-methyl-1-aziridinyl)phosphine oxide; pentaerythritol tris-3-(1-aziridinyl propionate); and pentaerythritol tetrakis-3-(1-aziridinyl propionate). Commercially available polyfunctional aziridines include those available under the trade designations xe2x80x9cXAMA-2xe2x80x9d (trimethylolpropane-tris-(.beta.-(N-aziridinyl)propionate) and xe2x80x9cXAMA-7xe2x80x9d (pentaerythritol-tris-(.beta.-(N-aziridinyl)propionate) from B.F. Goodrich Chemical Co., Cleveland, Ohio, and xe2x80x9cNeoCryl CX-100xe2x80x9d from Zeneca Resins, Wilmington, Mass.
The cross-linker will generally be used in an amount of 5 parts by weight to 15 parts by weight for 100 parts by weight of the polycarbonate-based polyurethane.
The polyurethane layer may contain further components conventionally employed in protective coatings such as for example an anti-oxidant or an Ultraviolet radiation stabilizer. Further, the polyurethane layer of the present invention can be pigmented if a particular tinting of the multilayer-layer sheet is desired. Although the addition of inorganic or organic pigments somewhat reduces the excellent properties of the polyurethane layer, they can be added to the polyurethane layer while still achieving a good and useful weatherability, chemical and heat resistance as well as a good abrasion and scratch resistance. Particularly preferred coloring pigments are dye pigments and most preferably aqueous borne dye pigments. Dye pigments suitable for the addition to the polyurethane layer may be in the form of a paste that comprises the dye pigment mixed with a water soluble or water dispersible binder. Commercially available dye pigments that can be used in the polyurethane layer of this invention include IsoversaI(trademark) WL available from ISL Chemie GmbH and the dye pigments available from BASF under the trade name Luconyl(trademark). Typically, dye pigments can be added to the polyurethane layer in an amount of 0,5 phr (parts per hundred) up to 10 phr without reducing the beneficial properties of the polyurethane layer to an unacceptable level.
A cross-linked polyurethane layer of the present invention typically has an E-modulus (also known as Young modulus) of at least 750 N/mm2, a tensile strength at break between 22 and 44 N/mm2 and an elongation at break of 30 to 140%.
The polyurethane layer of the present invention is provided on a polymeric film to obtain the multilayer sheet of the present invention. Polymeric films on which the polyurethane layer can be provided include polyurethane films, polyester films and polyolefin films such as polypropylene film, polyethylene films and films formed from blends of polyethylene and polypropylene, films formed from ethylene modified copolymers such as ethylene-vinylacetate, ethylene-(meth)acrylic acid, ethylene-methacrylate and blends of these materials. Polymeric films with particularly desirable properties for use in a multilayer sheet to protect the body of an automobile include the ionomers of olefin/vinyl carboxylate copolymers such as ethylene-acrylic acid and ethylene-methacrylic acid copolymers combined with various metal cations including cations of lithium, sodium, potassium, zinc, aluminum and calcium. Suitable commercial ionomer resins include the Surlyn(trademark) family of materials available from E.I. DuPont de Nemours and Co.
Polymeric films formed from ionomers of olefin/vinyl carboxylate copolymers have excellent optical characteristics, high flexibility, good heat resistance and desired shrinkage behavior. Combined with the polyurethane layer of this invention, a multilayer sheet results that has excellent protective properties for use in exterior applications.
In a preferred embodiment in connection with the present invention, the multilayer sheet further comprises an adhesive layer on the major side of the polymeric film opposite to the major side of the polymeric film carrying the polyurethane layer. The adhesive layer is generally protected by a conventional release liner. A suitable adhesive layer for use in this embodiment preferably includes a normally tacky pressure sensitive adhesive. The latter is being preferred in the present invention. Particularly suitable pressure sensitive adhesives are, for example, based on polyacrylates, synthetic and natural rubbers, polybutadiene and copolymers or polyisoprenes and copolymers. Silicone based adhesives such as polydimethylsiloxane and polymethylphenylsiloxane may also be used. Particularly preferred pressure sensitive adhesives for use in this invention are polyacrylate based adhesives because they provide such properties as high clarity, UV-stability and aging resistance. Polyacrylate adhesives that can be used in this invention include, for example, those described in U.S. Pat. No. 4,418,120; U.S. Pat. No. Re 24,906 (Ulrich), U.S. Pat. No. 4,619,867; U.S. Pat. No. 4,835,217 and WO 87/00189. Preferably, the polyacrylate pressure sensitive adhesive comprises a cross-linked copolymer of a C4-C12 alkylacrylate and an acrylic acid. The polyacrylate pressure sensitive adhesive preferably also comprises a tackifier such as rosin ester. Adhesives useful in the invention may incorporate additives such as ground glass, titanium dioxide, silica, glass beads, waxes, tackifiers, low molecular weight thermoplastics, oligomeric species, plasticizers, pigments, metallic flakes and metallic powders as long as they are provided in an amount that does not materially adversely effect the adhesive bond to the surface. Generally, the adhesive layer is provided at a thickness of 25 to 560 microns. For certain applications, such as applying the multilayer sheet to a car body, it is often desirable that the adhesive has an initial repositionability so that the sheet can be adjusted to fit at a desired place before a permanent bond is formed. Typically, such repositionability may be achieved by providing a layer of minute glass bubbles on the adhesive surface as disclosed in U.S. Pat. No. 3,331,729.
The multilayer sheet of the present invention can be obtained by coating a coating composition comprising the polycarbonate-based polyurethane on a major side of the polymeric film. Prior to coating, the polymeric film is preferably corona treated or alternatively, one or more primer layers may be provided on the polymeric film to assure good coatability and adherence of the polyurethane layer to the polymeric film. It is furthermore desirable to coat the polycarbonate-based polyurethane from an aqueous borne dispersion. By the term xe2x80x9caqueous bornexe2x80x9d is meant that the major part of the fluid phase of the dispersion consists of water. The fluid phase may further contain organic solvents, in particular water miscible solvents. Preferably, the fluid phase of the dispersion will contain at least 60% by weight and more preferably at least 80% by weight of water. The coating composition further contains the cross-linker and any other optional compounds such as dye pigments. The total amount of solids of the coating composition will typically vary between 25% by weight and 50% by weight. In connection with a preferred embodiment of the present invention, at least 80% by weight and more preferably between 90% by weight and 100% by weight of the solids will be formed by the polycarbonate-based polyurethane and the cross-linker. The coating composition will generally be applied in an amount sufficient to obtain a dried thickness of 5 to 15 microns.
Any conventional coating technique may be employed for coating the polyurethane coating composition on the polymeric film. Examples of useful coating techniques include meyer bar coating, spray coating, screen printing, rotary screen coating, as well as gravure coating such as direct (forward) gravure coating, reverse gravure coating and offset gravure coating.
Cross-linking of the coated polyurethane coating composition will generally be achieved by heating. Heating may be accomplished by supplying direct heat or indirectly for example by infrared radiation. Typically, the coating is heated to a temperature of 50xc2x0 C. to 140xc2x0 C., preferably 90xc2x0 C. to 125xc2x0 C. for 20 seconds to 5 minutes and preferably 20 seconds to 60 seconds to obtain a sufficient level of cross-linking of the polyurethane layer.
In accordance with a preferred embodiment in connection with the present invention, the opposite side of the polymeric film can be coated with an adhesive coating composition to provide an adhesive layer to the polymeric film. The adhesive coating composition may be solventless, solvent based or water based. As an alternative to coating, the adhesive layer may be laminated to the polymeric film. The adhesive layer may be provided after coating of the polyurethane coating composition to the polymeric film or prior to coating of the polyurethane coating composition.